pH-Switchable Inversion of the Metal-Centered Chirality of Metallabenzenes: Opposite Stereodynamics in Reactions of Ruthenabenzene with L- and D-Cysteine

Authors

  • Ran Lin,

    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Dr. Hong Zhang,

    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Dr. Shunhua Li,

    Corresponding author
    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    2. Key Laboratory of Analytical Science, Xiamen University, Xiamen 361005 (P.R. China)
    • State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Leiqi Chen,

    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Prof. Dr. Weiguang Zhang,

    1. School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (P.R. China)
    Search for more papers by this author
  • Prof. Dr. Ting Bin Wen,

    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Prof. Hui Zhang,

    Corresponding author
    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    • State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author
  • Prof. Dr. Haiping Xia

    Corresponding author
    1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    • State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (P.R. China), Fax: (+86) 592-2186628
    Search for more papers by this author

Abstract

We report herein the first study on the chemical interaction between metallabenzenes and bioactive molecules. Due to its unique stereoelectronic activities, a phenanthroline-derived ruthenabenzene [Ru{CHC(PPh3)CHC(PPh3)CH}Cl(C12H8N2)(PPh3)]Cl2 (1) selectively binds cysteine in aqueous solution at physiological pH and then undergoes a dynamic inversion of configuration at the Ru center. The structure of the L-cysteine-binding product of 1 has been determined by means of X-ray diffraction. The replacement of the L-cysteine with the D form results in an inverted stereodynamic effect. Furthermore, the inversion process of the Ru-centered configuration could be conveniently controlled by a simple pH adjustment. This is attributed to the significant influence of a special intramolecular electrostatic interaction on the dynamic epimerization process of the cysteine-binding product.

Ancillary